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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 73 records · Page 4

Selectively accessing the hotspots of optical nanoantennas by self-aligned dry laser ablation

Plasmonic nanostructures serve as optical antennas for concentrating the energy of incoming light in localized hotspots close to their surface. By positioning nanoemitters in the antenna hotspots, energy transfer is enabled, leading to novel hybrid antenna-emitter-systems, where the antenna can be used to manipulate the optical properties of the nano-objects. The challenge remains how to precisely position emitters within the hotspots. We report a self-aligned process based on dry laser ablation of a calixarene that enables the attachment of molecules within the electromagnetic hotspots at the tips of gold nanocones. Within the laser focus, the ablation threshold is exceeded in nanoscale volumes, leading to selective access of the hotspot areas. A first indication of the site-selective functionalization process is given by attaching fluorescently labelled proteins to the nanocones. In a second example, Raman-active molecules are selectively attached only to nanocones that were previously exposed in the laser focus, which is verified by surface enhanced Raman spectroscopy. Enabling selective functionalization is an important prerequisite e.g. for preparing single photon sources for quantum optical technologies, or multiplexed Raman sensing platforms.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Advances in Atomic Layer Deposition (ALD) Nanolaminate Synthesis of Thermoelectric Films in Porous Templates for Improved Seebeck Coefficient

Thermoelectrics is a green renewable energy technology which can significantly contribute to power generation due to its potential in generating electricity out of waste heat. The main challenge for the development of thermoelectrics is its low conversion efficiency. One key strategy to improve conversion efficiency is reducing the thermal conductivity of thermoelectric materials. In this paper, the state-of-the-art progresses made in improving thermoelectric materials are reviewed and discussed, focusing on phononic engineering via applying porous templates and ALD deposited nanolaminates structure. The effect of nanolaminates structure and porous templates on Seebeck coefficient, electrical conductivity and thermal conductivity, and hence in figure of merit zT of different types of materials system, including PnCs, lead chalcogenide-based nanostructured films on planar and porous templates, ZnO-based superlattice, and hybrid organic-inorganic superlattices, will be reviewed and discussed.

36 MATERIALS SCIENCE↗

Core-shell metallic alloy nanopillars-in-dielectric hybrid metamaterials with magneto-plasmonic coupling

Combining plasmonic and magnetic properties, namely magneto-plasmonic coupling, inspires great research interest and the search for magneto-plasmonic nanostructure becomes considerably critical. In this work, we designed a nanopillar-in-matrix structure with core–shell alloyed nanopillars for both BaTiO 3 (BTO)-Au 0.5 Co 0.5 (AuCo) and BTO-Au 0.25 Cu 0.25 Co 0.25 Ni 0.25 (AuCuCoNi) hybrid systems, i.e., ferromagnetic alloy cores (e.g., Co or CoNi) with plasmonic shells (e.g., Au or Au/Cu). These core–shell alloy nanopillars are uniformly embedded into a dielectric BTO matrix to form a vertically aligned nanocomposite (VAN) structure. Both hybrid systems present excellent epitaxial quality and interesting multi-functionality, e.g., high magnetic anisotropy, magneto-optical coupling response, tailorable plasmonic resonance wavelength, tunable hyperbolic properties and strong optical anisotropy. These alloyed nanopillars-in-matrix designs provide enormous potential for complex hybrid material designs with multi-functionality and demonstrate strong interface enabled magneto-plasmonic coupling along with plasmonic and magnetic performance.

36 MATERIALS SCIENCE↗

High optical transparent two-dimensional electronic conducting system and process for generating same

Hybrid transparent conducting materials are disclosed with combine a polycrystalline film and conductive nanostructures, in which the polycrystalline film is “percolation doped” with the conductive nanostructures. The polycrystalline film preferably is a single atomic layer thickness of polycrystalline graphene, and conductive nanostructures preferably are silver nanowires.

Alam, Muhammad Ashraful↗

High optical transparent two-dimensional electronic conducting system and process for generating same

Hybrid transparent conducting materials are disclosed which combine a polycrystalline film and conductive nanostructures, in which the polycrystalline film is “percolation doped” with the conductive nanostructures. The polycrystalline film preferably is a single atomic layer thickness of polycrystalline graphene, and the conductive nanostructures preferably are silver nanowires.

Alam, Muhammad Ashraful↗

Self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars

Oxide-metal-based hybrid materials have gained great research interest in recent years owing to their potential for multifunctionality, property coupling, and tunability. Specifically, oxide-metal hybrid materials in a vertically aligned nanocomposite (VAN) form could produce pronounced anisotropic physical properties, e.g., hyperbolic optical properties. Herein, self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars (as fine as 3 nm in diameter) embedded in a HfO 2 matrix were fabricated using a one-step self-assembly process. The film crystallinity and pillar uniformity can be obviously improved by adding an ultra-thin TiN-Au buffer layer during the growth. Here, the HfO 2 -Au hybrid VAN films show an obvious plasmonic resonance at 480 nm, which is much lower than the typical plasmonic resonance wavelength of Au nanostructures, and is attributed to the well-aligned ultra-fine Au nanopillars. Coupled with the broad hyperbolic dispersion ranging from 1050 nm to 1800 nm in wavelength, and unique dielectric HfO 2 , this nanoscale hybrid plasmonic metamaterial presents strong potential for the design of future integrated optical and electronic switching devices.

36 MATERIALS SCIENCE↗

Morphology and property tuning in ZnO–Ni hybrid metamaterials in vertically aligned nanocomposite (VAN) form

ZnO thin films have attracted significant interest in the past decades owing to their unique wide band gap properties, piezoelectric properties, non-linearity and plasmonic properties. Recent efforts have been made in coupling ZnO with secondary phases to enhance its functionalities, such as Au–ZnO nanocomposite thin films with tunable optical and plasmonic properties. In this work, magnetic nanostructures of Ni are incorporated in ZnO thin films in a vertically aligned nanocomposite (VAN) form to couple magnetic and plasmonic response in a complex hybrid metamaterial system. Nickel (Ni) is of interest due to its ferromagnetic and plasmonic properties along with gold (Au) which is also plasmonic. Therefore, two approaches, namely, tuning of the deposition pressure and use of a ZnO–Au seeding layer have been attempted to achieve unique Ni nanostructures in addition to tuning of the microstructure. Together, both approaches demonstrate a range of microstructures such as core–shell, nanodisk, nanocup, and nanocube-like morphologies not previously attempted. Additionally, there is effective tuning of properties. Specifically, the seeding layer thickness causes hyperbolic behavior as well as redshift in the surface plasmon resonance (SPR) wavelength. The addition of the ZnO–Au seeding layer directly influences the optical properties. Plus, regardless of the different approaches, the films demonstrate magnetic anisotropy based on the composition and microstructure of the film which impacted the saturation magnetization and coercivity. This study demonstrates the potential of ZnO-based complex hybrid metamaterials with coupled electro-magneto-optical properties for integrated photonic devices.

Bhatt, Nirali A. [Purdue Univ., West Lafayette, IN↗

Synergistic CuWO 4 /NiS 2 Binary Nanostructures for Efficient Photocatalytic Hydrogen Production

A viable and ecologically safe method for producing green hydrogen is photocatalytic hydrogen (H 2 ) production. However, the development of effective semiconductor materials with improved activity and long-term stability is still a major obstacle. Here, in this work, we report the development of a broadband-gap, UV light-responsive CuWO 4 /NiS 2 nanocomposite using simple hydrothermal and wet impregnation techniques. The hybrid systems, with photocatalytic presentation, were thoroughly assessed using spectroscopic, photophysical, and microscopic characterization methods. The optimized CuWO 4 /NiS 2 nanostructure demonstrated an impressive H 2 generation rate of 28.2 mmol h –1 g –1 under light irradiation, which is roughly 2.71 and 3.28 times greater than those of pristine CuWO 4 (10.4) and NiS 2 (8.6 mmol h -1 g (cat) -1 ), respectively. The enhanced presentation is ascribed to the synergetic interface between the coupled semiconductors, which facilitates the formation of a nanostructure. This arrangement inhibits electron–hole recombination and encourages effective charge carrier parting. Additionally, compared with pristine CuWO 4 and NiS 2 , respectively, the CuWO 4 /NiS 2 composite showed a noticeably greater photocurrent density. The developed nanostructured CuWO 4 /NiS 2 displayed a 28.6% quantum efficiency at 450 nm. These outcomes validate CuWO 4 /NiS 2 ’s significant aptitude as a non-noble-metal photocatalyst for the production of sustainable hydrogen.

CuWO4/NiS2↗

Fabrication and Assembly of Robust, Water-Soluble Molecular Interconnects via Encoded Hybridization (Final Report)

The major goals of this project include: i) the synthesis of sequence-specific oligo(peptoid)s bearing dynamic covalent pendant groups (i.e., amine, aldehyde boronic acid, and catechol) and characterization of the selective hybridization between these oligomers, where amines will reversibly interact with aldehydes and boronic acids with catechols; ii) the synthesis of dynamic covalent-bearing, trialkylsilane-protected 1,3- and 1,4-ethynyl phenylhalide monomers and their subsequent sequence-specific coupling via sequential Sonogashira ligation and fluoride-mediated silyl deprotection reactions to afford pi-conjugated oligo(phenylene-ethynylene)s; iii) templated, semi-conservative replication of dynamic covalent oligomers; and iv) characterization of the dynamic covalent hybridization of oligo(phenylene-ethynylene)s and the assembly of these oligomers into complex nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetically recyclable nanocomposites via lanthanide-based MOFs grown on natural sea sponge: Screening hydrogenation of nitrophenol to aminophenol

Catalysts have played a significant role in chemical industries and received significant attention as a result. Unfortunately, many common catalytic systems are comprised of a small number of elemental species or use similar synthetic strategies, which potentially limit innovation in areas such as the discovery of new transformations. Metal-organic frameworks (MOFs) have been established as versatile materials employed in various applications that include catalysis; however, the majority of MOFs have been synthesized using transition metal building blocks, possibly hindering advances towards innovative materials with unique properties. Here this work reports the synthesis of MOFs based on lanthanide elements (Ln = Ce, Gd, La, and Sm), which demonstrate great potential yet are often overlooked. The Ln-based MOFs were grown in situ on natural sea sponge supports and Fe ion containing solution, followed by a thermal carbonization treatment to generate FeLn metal nanoparticles (NPs) embedded on carbon support (FeLn@C). These nanostructured products exhibited good crystallinity and well-confined particle sizes. We then demonstrate that these hybrid materials can be used as effective heterogeneous nanocatalysts for the hydrogenation of nitrophenol to aminophenol in aqueous media. Besides, FeLn@C catalysts had a magnetic property due to Fe atoms in the NPs, which can be mechanically separated out from the aqueous solution since the catalysts are magnetically attracted to the external magnets. This magnetic recyclability combined with the usage of the natural materials highlight the importance of sustainability in the design of Ln-based MOFs and their catalytic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

0D-1D Hybrid Silicon Nanocomposite as Lithium-Ion Batteries Anodes

Lithium ion batteries (LIBs) are the enabling technology for many of the societal changes that are expected to happen in the following years. Among all the challenges for which LIBs are the key, vehicle electrification is one of the most crucial. Current battery materials cannot provide the required power densities for such applications and therefore, it makes necessary to develop new materials. Silicon is one of the proposed as next generation battery materials, but still there are challenges to overcome. Poor capacity retention is one of those drawbacks, and because it is tightly related with its high capacity, it is a problem rather difficult to address with common and scalable fabrication processes. Here we show that combining 0D and 1D silicon nanostructures, high capacity and stability can be achieved even using standard electrode fabrication processes. Capacities as high as 1200 mAh/g for more than 500 cycles at high current densities (2 A/g) were achieved with the produced hybrid 0D/1D electrodes. In this research, it was shown that while 0D nanostructures provide good strain relaxation capabilities, 1D nanomaterials contribute with enhanced cohesion and conductive matrix integrity.

0D↗

Nanostructured $\mathrm{GaAs/(Al,Ga)As}$ Waveguide for Low-Density Polariton Condensation from a Bound State in the Continuum

Exciton-polaritons are hybrid light-matter states that arise from strong coupling between an exciton resonance and a photonic cavity mode. As bosonic excitations, they can undergo a phase transition to a condensed state that can emit coherent light without a population inversion. This aspect makes them good candidates for thresholdless lasers, yet short exciton-polariton lifetime has made it difficult to achieve condensation at very low power densities. In this sense, long-lived symmetry-protected states are excellent candidates to overcome the limitations that arise from the finite mirror reflectivity of monolithic microcavities. In this work we use a photonic symmetry-protected bound state in the continuum coupled to an excitonic resonance to achieve state-of-the-art polariton condensation threshold in a GaAs/(Al,Ga)As waveguide. Most important, we show the influence of fabrication control and how surface passivation via atomic layer deposition provides a way to reduce exciton quenching at the grating sidewalls.

74 ATOMIC AND MOLECULAR PHYSICS↗

Impact of Nanoparticle Size and Surface Chemistry on Peptoid Self-Assembly

Self-assembled organic nanomaterials can be generated by bottom-up assembly pathways where the structure is controlled by the organic sequence and altered using pH, temperature, and solvation. In contrast, self-assembled structures based on inorganic nanoparticles typically rely on physical packing and drying effects to achieve uniform superlattices. By combining these two chemistries to access inorganic–organic nanostructures, we aim to understand the key factors that govern the assembly pathway and structural outcomes in hybrid systems. In this work, we outline two assembly regimes between quantum dots (QDs) and reversibly binding peptoids. These regimes can be accessed by changing the solubility and size of the hybrid (peptoid-QD) monomer unit. The hybrid monomers are prepared via ligand exchange and assembled, and the resulting assemblies are studied using ex-situ transmission electron microscopy as a function of assembly time. In aqueous conditions, QDs were found to stabilize certain morphologies of peptoid intermediates and generate a final product consisting of multilayers of small peptoid sheets linked by QDs. The QDs were also seen to facilitate or inhibit assembly in organic solvents based on the relative hydrophobicity of the surface ligands, which ultimately dictated the solubility of the hybrid monomer unit. Increasing the size of the QDs led to large hybrid sheets with regions of highly ordered square-packed QDs. A second, smaller QD species can also be integrated to create binary hybrid lattices. Furthermore, these results create a set of design principles for controlling the structure and structural evolution of hybrid peptoid-QD assemblies and contribute to the predictive synthesis of complex hybrid matter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Beyond Conventional Sensing: Hybrid Plasmonic Metasurfaces and Bound States in the Continuum

Fano resonances result from the strong coupling and interference between a broad background state and a narrow, almost discrete state, leading to the emergence of asymmetric scattering spectral profiles. Under certain conditions, Fano resonances can experience a collapse of their width due to the destructive interference of strongly coupled modes, resulting in the formation of bound states in the continuum (BIC). In such cases, the modes are simultaneously localized in the nanostructure and coexist with radiating waves, leading to an increase in the quality factor, which is virtually unlimited. In this work, we report on the design of a layered hybrid plasmonic-dielectric metasurface that facilitates strong mode coupling and the formation of BIC, resulting in resonances with a high quality factor. We demonstrate the possibility of controlling Fano resonances and tuning Rabi splitting using the nanoantenna dimensions. We also experimentally demonstrate the generalized Kerker effect in a binary arrangement of silicon nanodisks, which allows for the tuning of the collective modes and creates new photonic functionalities and improved sensing capabilities. Our findings have promising implications for developing plasmonic sensors that leverage strong light-matter interactions in hybrid metasurfaces.

36 MATERIALS SCIENCE↗

Nitride-Oxide-Metal Heterostructure with Self-Assembled Core–Shell Nanopillar Arrays: Effect of Ordering on Magneto-Optical Properties

Magneto-optical (MO) coupling incorporates photon-induced change of magnetic polarization that can be adopted in ultrafast switching, optical isolators, mode convertors, and optical data storage components for advanced optical integrated circuits. However, integrating plasmonic, magnetic, and dielectric properties in one single material system poses challenges since one natural material can hardly possess all these functionalities. Here, co-deposition of a three-phase heterostructure composed of a durable conductive nitride matrix with embedded core–shell vertically aligned nanopillars, is demonstrated. Additionally, the unique coupling between ferromagnetic NiO core and atomically sharp plasmonic Au shell enables strong MO activity out-of-plane at room temperature. Further, a template growth process is applied, which significantly enhances the ordering of the nanopillar array. The ordered nanostructure offers two schemes of spin polarization which result in stronger antisymmetry of Kerr rotation. The presented complex hybrid metamaterial platform with strong magnetic and optical anisotropies is promising for tunable and modulated all-optical-based nanodevices.

36 MATERIALS SCIENCE↗

Hierarchical thermal-conductive polymer nanocomposites for thermal management

Managing heat in electrical conductors is a major challenge to meet the demands for sustainable energy use and electrical reliability, most notably power electronics and energy-critical electrical machines. Achieving such disparate functionalities, such as high temperature thermal and electrical reliability, require rational design and manufacturing of thermal conductor material and its hierarchical structures. Here we present hierarchical thermal-conductive nanocomposites, consisting of nanostructured ceramic conformal coating and aligned ultrahigh molecular weight polyethylene fiber, to tailor heat dissipation in electric conductors. The hybrid aligned thermal interface exhibits a highly desirable temperature dependent anisotropic high thermal conductivity with 0.98W m –1 K –1 and dielectric strength with 3.4. In addition, electrically insulating thermal interfaces demonstrate high-performing and reliable electrical systems under the dynamic load conditions. The surface temperature of heterogeneous ceramic-polymer encapsulated conductor is 17.8 °C lower than that of polymer-encapsulated conductor at the same electrical load. Consequently, the findings shown here hold great promises for directing heat extraction in electrical machine systems, advancing thermal management for emerging electronic applications.

36 MATERIALS SCIENCE↗

Self-supported MoO 2 /MoS 2 nano-sheets embedded in a carbon cloth as a binder-free substrate for high-energy lithium–sulfur batteries

As one of the most prospective candidates for next-generation rechargeable batteries, lithium-sulfur (Li-S) batteries currently still encounter great challenges associated with the low conductivity, severe shuttle effects, and sluggish redox kinetics. Herein, a self-supported sulfur host is fabricated by an in-situ growth of MoO 2 /MoS 2 nano-sheets on a carbon cloth (CC). First, carbon cloth serves as a good template for the morphology-controlled synthesis of nanostructured materials, which not only alleviates the agglomeration of MoO2/MoS2, but also enhances the flexibility and mechanical strengthen of the hybrid architecture as a free-standing host. Second, the polysulfide-trapping ability can be greatly enhanced by both physical and chemical adsorption from the MoO 2 /MoS 2 -anchored carbon cloth. Moreover, the partially sulfurized MoO 2 /MoS 2 nano-sheets integrate the benefits of conductive MoO 2 and sulfiphilic MoS 2 , thus facilitating fast charge transfer and redox kinetics of polysulfide conversion. As a result, these attributes enable the host to hold a high sulfur loading (up to 7.6 mg cm -2 ), which exceeds most of the reported carbon cloth-related cathode work in the literature. Furthermore, the Li-S cells can achieve a high peak capacity of 1350 mA h g -1 , excellent rate capability (C/20 - 2C rate), impressive areal capacity (up to 6.3 mA h cm -2 ), and a high capacity retention of 85% after 100 cycles.

25 ENERGY STORAGE↗